EP0984859B1 - Lithographic imaging with constructions having mixed organic/inorganic layers - Google Patents

Lithographic imaging with constructions having mixed organic/inorganic layers Download PDF

Info

Publication number
EP0984859B1
EP0984859B1 EP99911401A EP99911401A EP0984859B1 EP 0984859 B1 EP0984859 B1 EP 0984859B1 EP 99911401 A EP99911401 A EP 99911401A EP 99911401 A EP99911401 A EP 99911401A EP 0984859 B1 EP0984859 B1 EP 0984859B1
Authority
EP
European Patent Office
Prior art keywords
layer
inorganic
ink
deposition material
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99911401A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0984859A1 (en
Inventor
Thomas E. Lewis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Presstek LLC
Original Assignee
Presstek LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Presstek LLC filed Critical Presstek LLC
Publication of EP0984859A1 publication Critical patent/EP0984859A1/en
Application granted granted Critical
Publication of EP0984859B1 publication Critical patent/EP0984859B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B41C1/1033—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials by laser or spark ablation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/20—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by inorganic additives, e.g. pigments, salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers

Definitions

  • the present invention relates to digital printing apparatus and methods, and more particularly to imaging of lithographic printing-plate constructions on- or off-press using digitally controlled laser output.
  • a printable image is present on a printing member as a pattern of ink-accepting (oleophilic) and ink-rejecting (oleophobic) surface areas. Once applied to these areas, ink can be efficiently transferred to a recording medium in the imagewise pattern with substantial fidelity.
  • Dry printing systems utilize printing members whose ink-rejecting portions are sufficiently phobic to ink as to permit its direct application. Ink applied uniformly to the printing member is transferred to the recording medium only in the imagewise pattern.
  • the printing member first makes contact with a compliant intermediate surface called a blanket cylinder which, in turn, applies the image to the paper or other recording medium.
  • the recording medium is pinned to an impression cylinder, which brings it into contact with the blanket cylinder.
  • the non-image areas are hydrophilic, and the necessary ink-repellency is provided by an initial application of a dampening (or "fountain") solution to the plate prior to inking.
  • the ink-abhesive fountain solution prevents ink from adhering to the non-image areas, but does not affect the oleophilic character of the image areas.
  • Plate-imaging devices amenable to computer control include various forms of lasers.
  • U.S. Patent Nos. 5,351,617 and 5,385,092 describe an ablative recording system that uses low-power laser discharges to remove, in an imagewise pattern, one or more layers of a lithographic printing blank, thereby creating a ready-to-ink printing member without the need for photographic development.
  • EP-A 0 825 021 and CA-A 2 221 922 describe a variety of lithographic plate configurations for use with such imaging apparatus.
  • the plate constructions include an inorganic layer (i.e., a metal, combination of metals, or a metal/non-metal compound) situated on an organic polymeric layer.
  • the inorganic layer ablates in response to imaging (e.g., infrared, or "IR") radiation.
  • the inorganic layer represents the topmost surface of the plate and accepts fountain solution, while the underlying polymeric layer accepts ink.
  • the inorganic layer serves only a radiation-absorption (rather than a lithographic) function, with the underlying layer accepting ink and an overlying layer either rejecting ink or accepting fountain solution.
  • Ablation of the inorganic layer by an imaging pulse generally weakens the topmost layer as well, and this; combined with disruption of its anchorage (due to disappearance of the ablated inorganic layer), renders the topmost layer easily removable in a post-imaging cleaning step.
  • polymeric layers may be selected (or applied as intermediate coatings) based on chemical compatibility with inorganic material.
  • a polymeric layer may also be pretreated (e.g., through plasma exposure) to modify the surface for greater interfacial compatibility with a subsequently applied inorganic layer.
  • Embodiments of present invention reduce the abruptness of interfacial transition by altering the effective properties of the organic layer (to which the inorganic layer is applied) by incorporating an inorganic component within the matrix of the organic layer.
  • an embodiment comprises a method of fabricating a lithographic printing plate having adjacent organic and inorganic layers.
  • a first layer comprising a curable polymer is softened, and an inorganic material -- compatible with or, in some cases, compositionally identical to -- the soon-to-be-applied inorganic layer is deposited onto a surface of the softened polymer.
  • the inorganic material overspreads the surface and integrates within the soft polymeric layer; at this point, it may be desirable to assist the migration of the inorganic material into the polymer (e.g., by charging the inorganic material and applying an opposite charge to a conductor underlying the polymer).
  • the polymer is then cured to immobilize the integrated deposition material, thereby forming a composite, and the desired inorganic layer is applied over the deposited inorganic material (and any exposed portions of the polymer).
  • This second inorganic layer, and possibly the previously. deposited inorganic material as well, is subject to ablative removal by exposure to laser radiation.
  • the second inorganic layer and the organic/inorganic composite have different affinities for ink and/or an ink-abhesive fluid.
  • the inorganic layer may, for example, be a metallic inorganic material as disclosed in EP-A 0 825 021 and CA-A 2 221 922. Despite the introduction of such an inorganic material within the matrix of the polymer, the natural affinity characteristics (e.g., oleophilicity) of the polymer may be retained.
  • the inorganic phase may have a pronounced effect on the stiffness and heat-transport properties of the composite, thereby enhancing physical compatibility with a pure inorganic layer, it may not significantly affect surface energy (so that the composite retains the affinity for ink and/or an ink-abhesive fluid that characterized the original polymer).
  • the deposition material may fully cover the surface of the polymeric material, forming a continuous layer thereover, or may instead form an intermittent pattern over the surface.
  • imaging radiation may remove both the second inorganic layer and the the deposition material from the polymer to expose the surface of the composite.
  • the polymer is generally chosen both for its lithographic affinity characteristics and also for its ability to be cured into a rigid, three-dimensional structure that permanently immobilizes the inorganic deposition material.
  • suitable for the present invention are polymeric materials that exhibit a low glass-transition temperature (which permits repeated, temperature-dependent transitions between soft and rigid states) unless provided with crosslinking groups that facilitate permanent cure (and thereby defeat further phase transitions).
  • the polymer comprises an acrylic polymer combined with a multifunctional acrylate monomer, which are crosslinked following deposition of the inorganic material. Acrylates, like many inorganic deposition materials, can be deposited under vacuum, permitting the entire fabrication process to be carried out in a single operation.
  • the deposition material will be ink-receptive and the second layer hydrophilic. This need not be the case, however, nor do these affinity characteristics mandate a wet plate.
  • the second layer can underlie a topcoat having a different affinity characteristic. Ablation of the second layer disrupts the anchorage of the topcoat, rendering it easily removed in a post-imaging cleaning step to reveal the deposition material (and possibly the polymeric layer as well).
  • the topcoat may be silicone or a fluoropolymer in the case of a dry plate, or a hydrophilic polymer if a polymer-topcoated wet plate is desired. of course, application of a polymeric layer over the inorganic second layer raises the same compatibility issues resolved through use of the inorganic deposition material.
  • a graded structure is built up on a substrate in successive deposition steps.
  • Both polymer precursors and an inorganic filler material are deposited in stages, with each stage containing a desired ratio of polymer to filler.
  • the proportion of filler increases in each stage, resulting in a concentration gradient with the amount of filler increasing away from the substrate.
  • the polymer precursors may be cured after each stage of deposition, permanently immobilizing the distribution of organic and inorganic material.
  • a top layer is applied over a surface of the structure, the top layer and the surface having different affinities for ink and/or an ink-abhesive fluid.
  • the top layer but not the underlying graded structure, may be subject to ablative removal by exposure to laser radiation.
  • the polymer precursor and the filler material may be deposited as a vapor or as a liquid.
  • the precursor is an acrylic polymer combined with a multifunctional acrylate monomer, the curing step crosslinking the monomers with the polymer.
  • the structure is typically oleophilic and the deposited inorganic layer hydrophilic, but the result need not be a wet plate.
  • a printing plate in accordance with the invention is selectively exposed, in a pattern representing an image, to imaging radiation (emanating, for example, from one or more lasers whose output is scanned over the surface of the plate) so as to ablate selected portions of the inorganic layer and, possibly, exposed portions of the deposition material, thereby directly producing an array of image features.
  • Ink is applied to the plate and transferred to a recording medium in the conventional fashion.
  • plate or “member” refers to any type of printing member or surface capable of recording an image defined by regions exhibiting differential affinities for ink and/or fountain solution; suitable configurations include the traditional planar lithographic plates that are mounted on the plate cylinder of a printing press, but can also include cylinders (e.g., the roll surface of a plate cylinder), an endless belt, or other arrangement.
  • Imaging apparatus suitable for use in conjunction with the present printing members includes at least one laser device that emits in the region of maximum plate responsiveness, i.e., whose lambda max closely approximates the wavelength region where the plate absorbs most strongly.
  • lasers that emit in the near-IR region are fully described in the '617 and '092 patents ; lasers emitting in other regions of the electromagnetic spectrum are well-known to those skilled in the art.
  • laser output can be provided directly to the plate surface via lenses or other beam-guiding components, or transmitted to the surface of a blank printing plate from a remotely sited laser using a fiber-optic cable.
  • a controller and associated positioning hardware maintains the beam output at a precise orientation with respect to the plate surface, scans the output over the surface, and activates the laser at positions adjacent selected points or areas of the plate.
  • the controller responds to incoming image signals corresponding to the original document or picture being copied onto the plate to produce a precise negative or positive image of that original.
  • the image signals are stored as a bitmap data file on a computer.
  • Such files may be generated by a raster image processor (RIP) or other suitable means.
  • a RIP can accept input data in page-description language, which defines all of the features required to be transferred onto the printing plate, or as a combination of page-description language and one or more image data files.
  • the bitmaps are constructed to define the hue of the color as well as screen frequencies and angles.
  • the imaging apparatus can operate on its own, functioning solely as a platemaker, or can be incorporated directly into a lithographic printing press. In the latter case, printing may commence immediately after application of the image to a blank plate, thereby reducing press set-up time considerably.
  • the imaging apparatus can be configured as a flatbed recorder or as a drum recorder, with the lithographic plate blank mounted to the interior or exterior cylindrical surface of the drum.
  • the exterior drum design is more appropriate to use in situ, on a lithographic press, in which case the print cylinder itself constitutes the drum component of the recorder or plotter.
  • the requisite relative motion between the laser beam and the plate is achieved by rotating the drum (and the plate mounted thereon) about its axis and moving the beam parallel to the rotation axis, thereby scanning the plate circumferentially so the image "grows" in the axial direction.
  • the beam can move parallel to the drum axis and, after each pass across the plate, increment angularly so that the image on the plate "grows" circumferentially. In both cases, after a complete scan by the beam, an image corresponding (positively or negatively) to the original document or picture will have been applied to the surface of the plate.
  • the beam is drawn across either axis of the plate, and is indexed along the other axis after each pass.
  • the requisite relative motion between the beam and the plate may be produced by movement of the plate rather than (or in addition to) movement of the beam.
  • the beam is scanned, it is generally preferable (for on-press applications) to employ a plurality of lasers and guide their outputs to a single writing array.
  • the writing array is then indexed, after completion of each pass across or along the plate, a distance determined by the number of beams emanating from the array, and by the desired resolution (i.e., the number of image points per unit length).
  • Off-press applications which can be designed to accommodate very rapid plate movement (e.g., through use of high-speed motors) and thereby utilize high laser pulse rates, can frequently utilize a single laser as an imaging source.
  • a printing plate 100 comprises a polymeric layer 102 and an inorganic layer 104.
  • a deposition material 106 is integrated within the matrix of polymer 102 and, covering all or much of the entire top surface thereof, provides a transition layer 106 s between layers 102 and 104. While material 106 may in fact be no more chemically compatible with the polymer of layer 102 than would be the inorganic material of layer 104, its physical integration within the matrix of layer 102 affords strong mechanical adhesion.
  • the surface layer 106s extends into the matrix of polymer 102 as a series of projections or "nails.”
  • the firmly anchored layer 106s is chemically compatible with inorganic layer 104 and therefore exhibits substantial adhesion to this layer.
  • Plate 100 may be manufactured as follows.
  • a substrate 110 which may be metal, plastic (e.g., polyester), paper, or some other durable graphic-arts material, accepts a coating of a polymeric material to form layer 102.
  • This polymeric material may, for example, be an acrylic polymer soluble in methyl ethyl ketone (MEK) and/or other solvents.
  • MEK methyl ethyl ketone
  • the acrylic polymer is combined with selected multifunctional acrylate monomers and coated (cast) from solvent onto substrate 110.
  • the multifunctional acrylate acts as a typical ester plasticizer, promoting adhesion and lowering the softening (melting) point of the polymer mixture.
  • the ACRYLOID acrylic polymers B-44, B-72, and B-82 supplied by Rohm & Haas, represent suitable solvent-soluble acrylics; dipentaerythritolpentaacrylate (e.g., the SR-399 product supplied by Sartomer) represents a suitable multifunctional acrylate.
  • the substrate-borne acrylic mixture is heated to the softening point, whereupon deposition material 106 is applied to the exposed surface thereof.
  • Material 106 may comprise one or more metals and/or metal alloys, intermetallics (i.e., two or more metals combined in a definite ratio), and/or compositions including one or more metals in combination with one or more nonmetals.
  • Preferred nonmetals for such compositions include boron, carbon, nitrogen, oxygen, fluorine, and silicon.
  • Material 106 may also be a hard inorganic compound such as silicon dioxide. It should be stressed that the deposition material can comprise a plurality of different substances fulfilling the foregoing criteria.
  • Material 106 may be applied by conventional roll (web) coating, or by intermittent-motion machines such as those employed for glass coating. Alternatively, material 106 may be applied by a vacuum coating process such as vacuum evaporation, electron-beam (EB) evaporation, or sputtering. The implementational details of such processes are well-characterized in the art.
  • the deposition process may involve controlled cooling to withdraw the latent heat resulting from condensation of the inorganic material from the vapor phase.
  • inorganic material 106 With the polymer 102 still in the softened state, it may be desirable to assist the migration of inorganic material 106 into polymer 102 in order to form the projections discussed above.
  • One approach is to statically charge the inorganic material 106 and apply an opposite charge to substrate 110.
  • Layer 102 is then cured, causing it to intensively crosslink and thereby "freeze" the inorganic material 106 to impart permanence.
  • An acrylate layer 102 can be cured by EB exposure.
  • the cured polymer exhibits substantially greater temperature resistance than the original, uncured polymer (that is, following cure, layer 102 can no longer be readily softened) and its solubility in the solvent(s) from which it was originally coated is substantially decreased, if not eliminated.
  • Layer 104 is then applied to the surface 106 s (which typically includes exposed portions of layer 102, since it is generally not necessary to ensure complete coverage of layer 102 by inorganic material 106), typically by vacuum deposition.
  • Layer 104 may, for example, be a very thin (50-500 ⁇ , with 300 ⁇ preferred for titanium) layer of a metal that may or may not develop a native oxide surface upon exposure to air. This layer ablates in response to IR radiation, and an image is imposed onto the plate through patterned exposure.
  • the metal or the oxide surface thereof exhibits hydrophilic properties that provide the basis for use of this construction as a lithographic printing plate.
  • Imagewise removal, by ablation, of layer 104 exposes surface 106 s ; if fully covered by inorganic material 106, this layer, too, may be ablated to expose the surface of composite layer 102.
  • the ultimately exposed layer is chosen for oleophilicity; accordingly, while layer 104 accepts fountain solution, layer 102 and/or inorganic material 106 reject fountain solution but accept ink.
  • the metal of layer 104 in this embodiment is at least one d-block (transition) metal, aluminum, indium or tin.
  • the metals are present as an alloy or an intermetallic.
  • layer 104 may be a hard, durable, hydrophilic, metallic inorganic layer comprising a compound of at least one metal with at least one non-metal, or a mixture of such compounds.
  • layer 104 ablatively absorbs imaging radiation, and consequently is applied at a thickness of only 10 - 200 nm (100-2000 ⁇ ).
  • the metal component of layer 104 in this form may be a d-block (transition) metal, an f-block (lanthanide) metal, aluminum, indium or tin, or a mixture of any of the foregoing (an alloy or, in cases in which a more definite composition exists, an intermetallic).
  • Preferred metals include titanium, zirconium, vanadium, niobium, tantalum, molybdenum and tungsten.
  • the non-metal component may be one or more of the p-block elements boron, carbon, nitrogen, oxygen and silicon.
  • a metal/non-metal compound in accordance herewith may or may not have a definite stoichiometry, and may in some cases (e.g., Al-Si compounds) be an alloy.
  • Preferred metal/non-metal combinations include TiN, TiON, TiO x (where 0.9 ⁇ x ⁇ 2.0), TiC, and TiCN.
  • an additional layer 112 can be applied over layer 104 to achieve different affinity or physical characteristics.
  • layer 112 may be a silicone or fluoropolymer material that rejects ink, thereby transforming construction 100 into a dry plate. During imaging, ablation of layer 104 disrupts the anchorage of layer 112, rendering it easily removed in a post-imaging cleaning step to reveal the surface 106 s or layer 102.
  • Useful materials for layer 112 and techniques of coating are disclosed in U.S. Patent Nos. 5,339,737 and Re. 35,512, the entire disclosures of which are hereby incorporated by reference. Basically, suitable silicone materials are applied using a wire-wound rod, then dried and heat-cured to produce a uniform coating deposited at, for example, 2 g/m 2 .
  • a second plate embodiment is shown in FIG. 2.
  • the construction 150 includes a graded layer 155 having a concentration of inorganic material 106 that increases with distance from substrate 110.
  • Layer 155 is built up in successive stages as follows.
  • a first coating 160 of polymeric material 102 is applied onto substrate 110, preferably either by vapor condensation or by coating.
  • layer 106 is deposited under vacuum, polymeric materials amenable to similar deposition conditions may be preferred for layer 102, allowing consecutive layers to be built up in multiple depositions within the same chamber or a linked series of chambers under common vacuum.
  • One suitable approach is detailed in U.S. Patent Nos.
  • an acrylate monomer is applied as a vapor under vacuum.
  • the monomer may be flash evaporated and injected into a vacuum chamber, where it condenses onto the surface.
  • the monomer is subsequently crosslinked by exposure to actinic (generally ultraviolet, or UV) radiation or an EB source.
  • acrylate materials include conventional monomers and oligomers (monoacrylates, diacrylates, methacrylates, etc.), as described at cols. 8-10 of the '446 patent, as well as acrylates chemically tailored for particular applications.
  • Representative monoacrylates include isodecyl acrylate, lauryl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated nonyl phenyl acrylate, isobornyl acrylate, tripropylene glycol methyl ether monoacrylate, and neopentyl glycol propoxylate methylether monoacrylate;
  • useful diacrylates include 1,6-hexaneciol diacrylate, tripropylene glycol diacrylate, polyethylene glycol (200) diacrylate, tetraethylene glycol diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, propoxylated neopentyl glycol diacrylate, the IRR-214 product supplied by UCB Radcure (aliphatic diacrylate monomer), propoxylated 1,6-hexanediol diacrylate, and ethoxylated 1,6-hexanediol di
  • acrylate-functional or other suitable resin coatings can be applied onto substrate 110 in routine fashion (under atmospheric conditions), according to techniques well-known in the art.
  • one or more acrylates are coated directly onto substrate 110 and later cured.
  • one or more acrylates is combined with a solvent (or solvents) and cast onto substrate 110, following which the solvent is evaporated and the deposited acrylate eventually cured. Volatile solvents, which promote highly uniform application at low coating weights, are preferred.
  • Acrylate coatings can also include non-acrylate functional compounds soluble or dispersible into an acrylate.
  • acrylate polymers are of course possible.
  • an energetic organic material such as an acetylene derivative, an azido or azide derivative, or a nitro-functional compound
  • gas -- typically explosively -- when the overlying inorganic layer 104 is heated.
  • the inorganic filler 106 is applied onto polymer 102 in a desired ratio relative to polymer 102.
  • polymer 102 accepts inorganic material 106 in a manner analogous to a thermally softened layer as described above.
  • material 106 can form a pattern of patches or islands over the surface layer 160, which is then cured as set forth above.
  • layer 160 by vapor condensation affords greater control over the pattern of deposition.
  • Polymer 102 can be applied under conditions that do not permit coalescence and consequent film formation, thereby allowing creation of a discontinuous polymer layer.
  • Inorganic material 106 is then deposited over the discontinuous pattern, so that the organic layer is effectively bound within the inorganic material rather than vice versa.
  • application of material 106 from vapor generally requires provision for removal of the latent heat of condensation.
  • the process is repeated for subsequent layers 162, 164, 166, which are applied with different ratios of inorganic material 106 to polymer material 102.
  • the proportion of inorganic material increases in each stage, resulting in a graded structure with the amount of inorganic material increasing away from substrate 110 as illustrated.
  • the composite layer 155 provides a gradual transition from an organic polymer to a mixed organic/inorganic material.
  • the dispersed islands of inorganic material can be made to occur in "units" (grains, particles, crystals, etc.) that are one or more orders of magnitude smaller than solids traditionally dispersed in organic binders as pigments.
  • layer 104 is applied as discussed above and, once again, an optional layer 112 can be added thereover.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Thermal Sciences (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
EP99911401A 1998-03-23 1999-03-17 Lithographic imaging with constructions having mixed organic/inorganic layers Expired - Lifetime EP0984859B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US7902198P 1998-03-23 1998-03-23
US79021P 1998-03-23
PCT/US1999/005613 WO1999048689A1 (en) 1998-03-23 1999-03-17 Lithographic imaging with constructions having mixed organic/inorganic layers

Publications (2)

Publication Number Publication Date
EP0984859A1 EP0984859A1 (en) 2000-03-15
EP0984859B1 true EP0984859B1 (en) 2003-05-28

Family

ID=22147909

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99911401A Expired - Lifetime EP0984859B1 (en) 1998-03-23 1999-03-17 Lithographic imaging with constructions having mixed organic/inorganic layers

Country Status (10)

Country Link
US (2) US6207349B1 (zh)
EP (1) EP0984859B1 (zh)
JP (1) JP3255648B2 (zh)
KR (1) KR100312395B1 (zh)
CN (2) CN1099345C (zh)
AU (1) AU729498B2 (zh)
CA (1) CA2290595C (zh)
DE (1) DE69908261T2 (zh)
TW (1) TW455549B (zh)
WO (1) WO1999048689A1 (zh)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6378432B1 (en) 2000-05-03 2002-04-30 Presstek, Inc. Lithographic imaging with metal-based, non-ablative wet printing members
US6605407B2 (en) * 2000-12-26 2003-08-12 Creo Inc. Thermally convertible lithographic printing precursor
US6589710B2 (en) * 2000-12-26 2003-07-08 Creo Inc. Method for obtaining a lithographic printing surface
WO2002070258A1 (en) 2001-03-01 2002-09-12 Presstek, Inc. Lithographic imaging with printing members having multiphase laser-responsive layers
US6715421B2 (en) 2001-03-01 2004-04-06 Presstek, Inc. Transfer imaging with metal-based receivers
DE10202991A1 (de) * 2002-01-26 2003-07-31 Roland Man Druckmasch Oberfläche für ein Bauteil einer Druckmaschine
EP1525093B1 (en) * 2002-07-30 2011-11-23 Kodak IL Ltd. Single-coat self-organizing multi-layered printing plate
CN1869277B (zh) 2002-08-02 2010-09-29 出光兴产株式会社 溅射靶、烧结体及利用它们制造的导电膜、有机el元件及其所用的衬底
US8691371B2 (en) * 2002-09-11 2014-04-08 General Electric Company Barrier coating and method
US8704211B2 (en) * 2004-06-30 2014-04-22 General Electric Company High integrity protective coatings
US6840175B2 (en) 2002-11-20 2005-01-11 Flint Ink Corporation Lithographic printing method using a single fluid ink
JP2005280073A (ja) * 2004-03-29 2005-10-13 Fuji Photo Film Co Ltd 平版印刷版の露光処理方法及びこの方法を実施する装置
GB2418628B (en) * 2004-10-01 2006-12-13 Acktar Ltd Improved laminates and the manufacture thereof
US20070148346A1 (en) * 2005-12-23 2007-06-28 General Electric Company Systems and methods for deposition of graded materials on continuously fed objects
JP5900155B2 (ja) * 2011-09-06 2016-04-06 株式会社村田製作所 流体制御装置
US9731456B2 (en) 2013-03-14 2017-08-15 Sabic Global Technologies B.V. Method of manufacturing a functionally graded article
WO2017196354A1 (en) * 2016-05-12 2017-11-16 Hewlett-Packard Development Company, L.P. Fabric print media
US20200338920A1 (en) * 2018-03-19 2020-10-29 Hewlett-Packard Development Company, L.P. Fabric printable medium

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4482622A (en) 1983-03-31 1984-11-13 Xerox Corporation Multistage deposition process
US4842893A (en) 1983-12-19 1989-06-27 Spectrum Control, Inc. High speed process for coating substrates
US4490774A (en) 1983-12-19 1984-12-25 General Electric Company Capacitors containing polyfunctional acrylate polymers as dielectrics
US5032461A (en) 1983-12-19 1991-07-16 Spectrum Control, Inc. Method of making a multi-layered article
US4647818A (en) 1984-04-16 1987-03-03 Sfe Technologies Nonthermionic hollow anode gas discharge electron beam source
EP0242460A1 (en) 1985-01-18 1987-10-28 SPECTRUM CONTROL, INC. (a Pennsylvania corporation) Monomer atomizer for vaporization
US4954371A (en) 1986-06-23 1990-09-04 Spectrum Control, Inc. Flash evaporation of monomer fluids
US4883731A (en) 1988-01-04 1989-11-28 Xerox Corporation Imaging system
US5176947A (en) * 1990-12-07 1993-01-05 International Business Machines Corporation Electroerosion printing plates
US5102756A (en) 1990-12-31 1992-04-07 Xerox Corporation Camera speed printing plate with in situ mask
US5260095A (en) 1992-08-21 1993-11-09 Battelle Memorial Institute Vacuum deposition and curing of liquid monomers
US5440446A (en) 1993-10-04 1995-08-08 Catalina Coatings, Inc. Acrylate coating material
US5440987A (en) * 1994-01-21 1995-08-15 Presstek, Inc. Laser imaged seamless lithographic printing members and method of making
US5681615A (en) 1995-07-27 1997-10-28 Battelle Memorial Institute Vacuum flash evaporated polymer composites
US5704291A (en) * 1996-01-30 1998-01-06 Presstek, Inc. Lithographic printing members with deformable cushioning layers
US5807658A (en) * 1996-08-20 1998-09-15 Presstek, Inc. Self-cleaning, abrasion-resistant, laser-imageable lithographic printing contructions

Also Published As

Publication number Publication date
AU729498B2 (en) 2001-02-01
CN1229223C (zh) 2005-11-30
EP0984859A1 (en) 2000-03-15
CA2290595C (en) 2004-06-15
DE69908261T2 (de) 2004-03-25
KR100312395B1 (ko) 2001-11-03
JP2000513289A (ja) 2000-10-10
US6300040B1 (en) 2001-10-09
CA2290595A1 (en) 1999-09-30
US6207349B1 (en) 2001-03-27
TW455549B (en) 2001-09-21
CN1272080A (zh) 2000-11-01
WO1999048689A1 (en) 1999-09-30
CN1446687A (zh) 2003-10-08
JP3255648B2 (ja) 2002-02-12
CN1099345C (zh) 2003-01-22
KR20010012825A (ko) 2001-02-26
AU3004999A (en) 1999-10-18
DE69908261D1 (de) 2003-07-03

Similar Documents

Publication Publication Date Title
EP0984859B1 (en) Lithographic imaging with constructions having mixed organic/inorganic layers
US5996498A (en) Method of lithographic imaging with reduced debris-generated performance degradation and related constructions
AU688702B2 (en) Lithographic printing plates for use with laser-discharge imaging apparatus
CA2143808C (en) Lithographic printing members for use with laser-discharge imaging apparatus
EP0914965A2 (en) Lithographic printing plates for use with laser-discharge imaging apparatus
US6279476B1 (en) Lithographic imaging with constructions having inorganic oleophilic layers
US6484637B2 (en) Lithographic imaging with printing members having enhanced-performance imaging layers
EP0974456B1 (en) Method of lithographic imaging with reduced debris-generated performance degradation and related constructions
US6006667A (en) Method of lithographic imaging with reduced debris-generated performance degradation and related constructions
CA2442421C (en) Lithographic imaging with constructions having mixed organic/inorganic layers
US6087069A (en) Lithographic imaging and cleaning of printing members having boron ceramic layers
WO2000015435A1 (en) Lithographic imaging with constructions having inorganic oleophilic layers
AU2121199A (en) Lithographic printing plates for use with laser-discharge imaging apparatus

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19991119

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB IT

17Q First examination report despatched

Effective date: 20010918

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB IT

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69908261

Country of ref document: DE

Date of ref document: 20030703

Kind code of ref document: P

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20040302

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20090330

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100317

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20120406

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20120330

Year of fee payment: 14

Ref country code: GB

Payment date: 20120326

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20130327

Year of fee payment: 15

BERE Be: lapsed

Owner name: *PRESSTEK INC.

Effective date: 20130331

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20130317

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20131129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130402

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130331

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130317

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69908261

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69908261

Country of ref document: DE

Effective date: 20141001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141001